CN101928210B - Method for preparing acyl chloride from silicon tetrachloride - Google Patents
Method for preparing acyl chloride from silicon tetrachloride Download PDFInfo
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- CN101928210B CN101928210B CN 201010235943 CN201010235943A CN101928210B CN 101928210 B CN101928210 B CN 101928210B CN 201010235943 CN201010235943 CN 201010235943 CN 201010235943 A CN201010235943 A CN 201010235943A CN 101928210 B CN101928210 B CN 101928210B
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- silicon tetrachloride
- acyl chloride
- acyl chlorides
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- chloride
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Abstract
The invention discloses a method for preparing acyl chloride from silicon tetrachloride, which belongs to the field of silicon tetrachloride application. The method comprises the following steps of: reacting the silicon tetrachloride serving as a bran-new acyl chlorination reagent with carboxylic acid under a certain condition to generate the acyl chloride; and separating the acyl chloride by using other products by a method of distillation or extraction and the like to obtain the acyl chloride, or directly utilizing the produced acyl chloride to react with other raw materials to prepare the product. The method has the characteristics of producing the acyl chloride with a high additional value by effectively converting the silicon tetrachloride which is the byproduct produced largely in the production process of polycrystalline silicon and organic silicon, transforming the byproduct silicon tetrachloride, which is difficult to manage, caused by the production development of the polycrystalline silicon and obviously reducing the cost for preparing the acyl chloride.
Description
Technical field
The present invention relates to a kind of method with preparing acyl chloride from silicon tetrachloride.
Background technology
Silicon tetrachloride is the sub product during production of polysilicon and organosilicon are produced at present.A large amount of by-produced tetrachlorosilanes in the production of polysilicon particularly, 20 tons of the general by-produced tetrachlorosilanes of one ton of polysilicon of every production.And silicon tetrachloride is highly toxic material, if just discharge and bury without handling, with serious environment pollution, and not even a blade of grass grows with burying ground to make discharging ground.The method of silicon tetrachloride conversion at present mainly contains: produce thermal silica, produce organosilicon product, produce optical fiber, be converted into trichlorosilane etc.Their basic characteristics are the silicon that utilizes in the silicon tetrachloride.
Acyl chlorides is a kind of important carboxylic acid derivative, at aspects such as organic synthesis, medicine are synthetic important use is arranged, mainly can take place hydrolysis, alcoholysis, ammonia (amine) separate, with multiple reactions such as organometallic reagent reaction, reduction reaction, α-hydrohalogenation.Acyl chlorides is one of the most active acylting agent.The domestic method of preparation acyl chlorides mainly contains at present:
1). the sulfur oxychloride method
In the presence of catalyzer, organic carboxyl acid and sulfur oxychloride generate acyl chlorides.Its advantage is that reaction conditions is gentle, room temperature or a little heat can react; Other are gas to product except that acyl chlorides, often need not purify and can use, and purity is good, and productive rate is high.Shortcoming is if the boiling point of acyl chlorides boiling point that generates and sulfur oxychloride is close then not easily separated with sulfur oxychloride; And the sulfur oxychloride consumption is big, and manufacturing cost is high, and equipment corrosion is serious.
2). the phosphorus trichloride method
Organic carboxyl acid and phosphorus trichloride reaction generate acyl chlorides and phosphorous acid.It is applicable to preparation lower boiling acyl chlorides, because the phosphorous acid that reaction generates is not volatile, can conveniently steam acyl chlorides.
3). the phosphorus pentachloride method
Organic carboxyl acid and phosphorus pentachloride reaction generate acyl chlorides and POCl3 etc.It is applicable to preparation high boiling point acyl chlorides, so that a POCl3 that generates obtains acyl chlorides after steaming.
4). the TRIPHOSGENE 99.5 method
Organic carboxyl acid and TRIPHOSGENE 99.5 reaction generate acyl chlorides and carbonic acid gas and hydrogenchloride.The TRIPHOSGENE 99.5 fusing point is high, and volatility is low, and reaction preference is strong, and yield is high, and is safe and convenient to use.But manufacturing cost is high, and equipment corrosion is serious.
5). the oxalyl chloride method
In the presence of catalyzer, oxalyl chloride and organic carboxyl acid reaction generate acyl chlorides.Oxalyl chloride can be by oxalic acid and phosphorus pentachloride prepared in reaction.
Other also have phosgenation, trichloromethylchloroformate method, carbon tetrachloride method, hexachloroacetone method etc.
On the other hand; Acyl chlorides; As a kind of important reaction intermediate, at aspects such as organic synthesis, medicine are synthetic important use is arranged, mainly can take place hydrolysis, alcoholysis, ammonia (amine) separate, with multiple reactions such as organometallic reagent reaction, reduction reaction, α-hydrohalogenation.Acyl chlorides is one of the most active acylting agent.The preparation method of acyl chlorides mainly contains at present: sulfur oxychloride method, phosphorus trichloride method, phosphorus pentachloride method, TRIPHOSGENE 99.5 method etc.Their basic characteristics are that the chloride reagent cost is high, are ten to 20 times of silicon tetrachloride at present like the price of phosphorus trichloride, if can utilize the chlorine in the silicon tetrachloride, are converted into acyl chlorides through certain chemical reaction, will be a kind of new ways that silicon tetrachloride is used.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the high industrial chemicals acyl chlorides of added value when transforming silicon tetrachloride.
The technical scheme that the present invention solves the problems of the technologies described above is: a kind of method with preparing acyl chloride from silicon tetrachloride,, reacted 2～4 hours down at 60-70 ℃ as chloride reagent with silicon tetrachloride with carboxylic acid, and generate acyl chlorides, its primitive reaction is:
4R-COOH+SiCl
4＝4R-COCl+Si(OH)
4。
As preferably: the add-on of said carboxylic acid and silicon tetrachloride, meter is 1: (1.1-2.5) in molar ratio.
As preferably: when silicon tetrachloride and carboxylic acid react; Recycle the excessive silicon tetrachloride and the hydrogenchloride of generation; Thereby can guarantee the security of entire reaction, otherwise the hydrogenchloride of evaporable silicon tetrachloride and generation will bring serious toxic to pollute.
As preferably: after generating acyl chlorides, acyl chlorides is separated with other products, obtain acyl chlorides.
Preferred as further: that acyl chlorides and the isolating method of other products are distillation or extraction; Also can directly utilize the acyl chlorides and other raw material reaction preparing products of generation; Its primitive reaction is:
R-COCl+X＝A
A is for using other products of the acyl chlorides production that generates.
Beneficial effect of the present invention is: present method is with silicon tetrachloride as a kind of brand-new chloride reagent under certain condition and carboxylic acid reaction, generates acyl chlorides.Through methods such as distillation or extractions acyl chlorides is separated with other products, obtain acyl chlorides.Perhaps directly utilize the acyl chlorides and other raw material reaction preparing products that produces.The characteristics of present method are the silicon tetrachlorides that has effectively transformed a large amount of by-products in production of polysilicon and the organosilicon production, produce the acyl chlorides with high added value; In conversion processing in the silicon tetrachloride as by-product that is difficult to administer that brings of production of polysilicon development, significantly reduced the cost of preparation acyl chlorides.
Embodiment
Below in conjunction with embodiment the present invention is made further detailed description.But should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1: the preparation of lauroyl chloride
In the acid-resistant reacting kettle that backflow and whipping appts are arranged, add a certain amount of LAURIC ACID 99 MIN, heat fused added silicon tetrachloride, and reacted 4 hours down at 60 ℃ in 1: 1.1 in molar ratio.Recycle the excessive silicon tetrachloride and the hydrogenchloride of generation simultaneously.
Greater than 70 ℃ of distillations down, steam excessive silicon tetrachloride earlier.Decompression steams lauroyl chloride under 1～2.4KPa, 130～150 ℃.
Embodiment 2: the preparation of lauroyl chloride
In the acid-resistant reacting kettle that backflow and whipping appts are arranged, add a certain amount of LAURIC ACID 99 MIN, heat fused added silicon tetrachloride in 1: 2.0 in molar ratio, reacted 3 hours down at 65 ℃, recycled the excessive silicon tetrachloride and the hydrogenchloride of generation simultaneously.
Greater than 70 ℃ of down distillations, steam excessive silicon tetrachloride earlier, decompression steams lauroyl chloride under 1～2.4KPa, 130～150 ℃.
Embodiment 3: the preparation of lauroyl chloride
In the acid-resistant reacting kettle that backflow and whipping appts are arranged, add a certain amount of LAURIC ACID 99 MIN, heat fused added silicon tetrachloride in 1: 2.5 in molar ratio, reacted 2 hours down at 70 ℃, recycled the excessive silicon tetrachloride and the hydrogenchloride of generation simultaneously.
Greater than 70 ℃ of down distillations, steam excessive silicon tetrachloride earlier, decompression steams lauroyl chloride under 1～2.4KPa, 130～150 ℃.
Embodiment 4: NSC 8882 synthetic
In the acid-resistant reacting kettle that backflow and whipping appts are arranged, add a certain amount of caproic acid, added silicon tetrachloride, and reacted 2 hours down in 1: 1.1 in molar ratio at 70 ℃.Recycle the excessive silicon tetrachloride and the hydrogenchloride of generation simultaneously.Heat up,, steam excessive silicon tetrachloride greater than 70 ℃ of distillations.Cool to room temperature slowly adds equimolar ethanol, reclaims hydrogenchloride and reaction heat.After reaction is accomplished, add water and stir, stratified liquid, the upper strata obtains the NSC 8882 first product.The NSC 8882 first product is washed with saturated aqueous sodium carbonate, and Hydrogen chloride is washed, and the washing after drying obtains pure NSC 8882.
Embodiment 5: NSC 8882 synthetic
In the acid-resistant reacting kettle that backflow and whipping appts are arranged, add a certain amount of caproic acid, added silicon tetrachloride, and reacted 3 hours down in 1: 1.8 in molar ratio at 65 ℃.Recycle the excessive silicon tetrachloride and the hydrogenchloride of generation simultaneously, heat up,, steam excessive silicon tetrachloride greater than 70 ℃ of distillations down.Cool to room temperature slowly adds equimolar ethanol, reclaims hydrogenchloride and reaction heat.After reaction is accomplished, add water and stir, stratified liquid, the upper strata obtains the NSC 8882 first product.The NSC 8882 first product is washed with saturated aqueous sodium carbonate, and Hydrogen chloride is washed, and the washing after drying obtains pure NSC 8882.
Embodiment 6: NSC 8882 synthetic
In the acid-resistant reacting kettle that backflow and whipping appts are arranged, add a certain amount of caproic acid, added silicon tetrachloride, and reacted 4 hours down in 1: 2.5 in molar ratio at 60 ℃; Recycle the excessive silicon tetrachloride and the hydrogenchloride of generation simultaneously; Heat up,, steam excessive silicon tetrachloride greater than 70 ℃ of distillations.Cool to room temperature slowly adds equimolar ethanol, reclaims hydrogenchloride and reaction heat.After reaction is accomplished, add water and stir, stratified liquid, the upper strata obtains the NSC 8882 first product.The NSC 8882 first product is washed with saturated aqueous sodium carbonate, and Hydrogen chloride is washed, and the washing after drying obtains pure NSC 8882.
Embodiment 7: ethyl n-butyrate synthetic
In the acid-resistant reacting kettle that backflow and whipping appts are arranged, add a certain amount of butyric acid, added silicon tetrachloride in 1: 1.1 in molar ratio, reacted 4 hours down, recycle the excessive silicon tetrachloride and the hydrogenchloride of generation simultaneously at 70 ℃.Heat up,, steam excessive silicon tetrachloride greater than 70 ℃ of distillations.Cool to room temperature slowly adds equimolar ethanol, reclaims hydrogenchloride.After reaction is accomplished, add water and stir, stratified liquid, the upper strata obtains the ethyl n-butyrate first product.The ethyl n-butyrate first product is washed with saturated aqueous sodium carbonate, and Hydrogen chloride is washed, and the washing after drying obtains pure ethyl n-butyrate.
Embodiment 8: ethyl n-butyrate synthetic
In the acid-resistant reacting kettle that backflow and whipping appts are arranged, add a certain amount of butyric acid, added silicon tetrachloride in 1: 2.0 in molar ratio, reacted 3 hours down, recycle the excessive silicon tetrachloride and the hydrogenchloride of generation simultaneously at 65 ℃.Heat up,, steam excessive silicon tetrachloride greater than 70 ℃ of distillations.Cool to room temperature slowly adds equimolar ethanol, reclaims hydrogenchloride.After reaction is accomplished, add water and stir, stratified liquid, the upper strata obtains the ethyl n-butyrate first product, and the ethyl n-butyrate first product is washed with saturated aqueous sodium carbonate, and Hydrogen chloride is washed, and the washing after drying obtains pure ethyl n-butyrate.
Embodiment 9: ethyl n-butyrate synthetic
In the acid-resistant reacting kettle that backflow and whipping appts are arranged, add a certain amount of butyric acid, added silicon tetrachloride, and reacted 4 hours down in 1: 2.5 in molar ratio at 60 ℃; Recycle the excessive silicon tetrachloride and the hydrogenchloride of generation simultaneously.Heat up,, steam excessive silicon tetrachloride greater than 70 ℃ of distillations.Cool to room temperature slowly adds equimolar ethanol, reclaims hydrogenchloride.After reaction is accomplished, add water and stir, stratified liquid, the upper strata obtains the ethyl n-butyrate first product, and the ethyl n-butyrate first product is washed with saturated aqueous sodium carbonate, and Hydrogen chloride is washed, and the washing after drying obtains pure ethyl n-butyrate.
Claims (4)
1. method with preparing acyl chloride from silicon tetrachloride is characterized in that: with silicon tetrachloride as chloride reagent, with carboxylic acid 60-70 ℃ of reaction 2～4 hours down, generate acyl chlorides, its primitive reaction is:
4?R-COOH+SiCl
4 = 4?R-COCl+Si(OH)
4；
During reaction, the add-on of said carboxylic acid and silicon tetrachloride, meter is 1: (1.1-2.5) in molar ratio;
Said R-COOH is a kind of in LAURIC ACID 99 MIN, caproic acid, the butyric acid.
2. the method with preparing acyl chloride from silicon tetrachloride according to claim 1 is characterized in that: when silicon tetrachloride and carboxylic acid react, recycle the excessive silicon tetrachloride and the hydrogenchloride of generation.
3. the method with preparing acyl chloride from silicon tetrachloride according to claim 1 is characterized in that: after generating acyl chlorides, acyl chlorides is separated with other products, obtain acyl chlorides.
4. the method with preparing acyl chloride from silicon tetrachloride according to claim 3 is characterized in that: acyl chlorides and the isolating method of other products are distillation or extraction.
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| CN105777531A (en) * | 2015-12-28 | 2016-07-20 | 四川理工学院 | Method for preparing cinnamoyl chloride from silicon tetrachloride |
| CN105601501A (en) * | 2016-02-29 | 2016-05-25 | 四川理工学院 | Method of preparing trichloro-acetic chloride from silicon tetrachloride |
| CN111848392B (en) * | 2020-07-17 | 2022-04-26 | 青岛科技大学 | Process for preparing paraphthaloyl chloride |
| CN115159909B (en) * | 2022-08-05 | 2023-03-31 | 南通宏宇建材科技有限公司 | Rice hull-based environment-friendly thermal insulation mortar and preparation method thereof |
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| EP1382716A2 (en) * | 2002-07-18 | 2004-01-21 | Air Products And Chemicals, Inc. | Method for etching high dielectric constant materials and for cleaning deposition chambers for high dielectric constant materials |
| CN1508115A (en) * | 2002-12-13 | 2004-06-30 | 上海群力化工有限公司 | High-purity benzoyl chloride synthesizing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1382716A2 (en) * | 2002-07-18 | 2004-01-21 | Air Products And Chemicals, Inc. | Method for etching high dielectric constant materials and for cleaning deposition chambers for high dielectric constant materials |
| CN1508115A (en) * | 2002-12-13 | 2004-06-30 | 上海群力化工有限公司 | High-purity benzoyl chloride synthesizing process |
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| 曲大伟.芳香酰氯的合成方法.《化学中间体》.2007,(第9期), |
| 芳香酰氯的合成方法;曲大伟;《化学中间体》;20071231(第9期);第18-19页第1.3节 * |
| 苯甲酰氯的合成与应用;赵美法等;《辽宁化工》;19980531;第27卷(第3期);第166页第4.2-4.3节 * |
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